US9765207B2 - Polymer microparticle-dispersed resin composition and method for producing same - Google Patents

Polymer microparticle-dispersed resin composition and method for producing same Download PDF

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US9765207B2
US9765207B2 US13/997,745 US201113997745A US9765207B2 US 9765207 B2 US9765207 B2 US 9765207B2 US 201113997745 A US201113997745 A US 201113997745A US 9765207 B2 US9765207 B2 US 9765207B2
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resin composition
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Yoshio Furukawa
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Kaneka Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/16—Solid spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10—Latex
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a polymer microparticle-dispersed resin composition, specifically, a polymer microparticle-dispersed resin composition in which polymer microparticles including a crosslinked polymer layer are dispersed in a resin.
  • Thermosetting resins such as epoxy resins, vinyl ester resins, unsaturated polyester resins, phenolic resins, bismaleimide resins, and cyanate resins are used in a wide range of applications in various fields because of their excellent features such as heat resistance, mechanical strength, and dimensional accuracy.
  • epoxy resins which are excellent in many respects including mechanical strength, electrical insulation properties, heat resistance, and adhesion, are used in various applications including construction materials, electrical and electronic materials, adhesives, and fiber reinforced composite materials.
  • cured products thereof have low fracture toughness, and may show extreme brittleness. Their brittleness is problematic in various applications.
  • improvement in the toughness of resins improvement in the impact resistance has also been demanded in recent years.
  • Another proposed method is to use rubbery polymer microparticles that are previously prepared as particles in an aqueous medium by a polymerization technique such as emulsion polymerization or suspension polymerization, and are substantially insoluble in an epoxy resin composition (e.g. Patent Literatures 2 and 3).
  • a polymerization technique such as emulsion polymerization or suspension polymerization
  • an epoxy resin composition e.g. Patent Literatures 2 and 3
  • Still another proposed method is to add crosslinked polymer microparticles that are free of rubber components to an epoxy resin composition (e.g. prior art document 1).
  • This method improves the fracture toughness almost or completely without degrading the elastic modulus and heat resistance.
  • a disadvantage of this strategy is that addition of such crosslinked polymer microparticles does not improve the impact resistance of the resin.
  • the present invention is made in view of the above-mentioned problems, and an object of the present invention is to provide a polymer microparticle-dispersed resin composition having an excellent elastic modulus (rigidity), heat resistance, toughness, and impact resistance in a good balance and that can be a novel method for modifying resin, and a method for preparing such a polymer microparticle-dispersed resin composition.
  • the present inventors intensively studied and found that a specifically structured polymer microparticle-dispersed resin composition exceeds the expectations based on the common theories, and the use of such a polymer microparticle-dispersed resin composition provides a cured product or a polymerized product that has improved fracture toughness and impact strength almost or completely without degrading the elastic modulus (rigidity and hardness) and heat resistance.
  • the present inventors completed the present invention. Additionally, the present inventors found a method for preparing the specifically structured polymer microparticle-dispersed composition of the present invention.
  • the present invention provides a polymer microparticle-dispersed resin composition, containing: 100 parts by weight of a resin; and 0.1 parts by weight to 150 parts by weight of polymer microparticles each including at least two layers including a crosslinked polymer layer and a coating polymer layer,
  • the resin composition having a particle dispersity of the polymer microparticles in the resin of not lower than 50%
  • the coating polymer layer contains a monomer containing a polymerizable or curable functional group, and the functional group is at least one selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, a carbon-carbon double bond, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester group, a cyclic amide group, a benzoxazine group, and a cyanate ester group.
  • the functional group is at least one selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, a carbon-carbon double bond, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester group, a cyclic amide group, a benzoxazine group, and a cyanate ester group.
  • the resin is at least one selected from the group consisting of curable monomers, polymerizable monomers, curable oligomers, polymerizable oligomers, and thermoplastic polymers.
  • the monomers or oligomers are organic compounds containing a polymerizable or curable functional group.
  • the present invention further relates to a method for preparing the polymer microparticle-dispersed resin composition, which includes: a first step of mixing an aqueous medium dispersion containing the polymer microparticles dispersed in an aqueous medium with an organic solvent having a water solubility at 20° C.
  • the present invention further relates to a prepreg, including: the polymer microparticle-dispersed resin composition of the present invention; and reinforcing fibers.
  • the present invention further relates to a fiber reinforced composite material, including a resin and reinforcing fibers, the material being obtained by curing the polymer microparticle-dispersed resin composition of the present invention.
  • polymer microparticle-dispersed resin composition of the present invention polymer microparticles having a specific structure are dispersed in a specific state in a resin. This enables cured products and polymerized products of the composition to have remarkably improved toughness and impact strength almost or completely without degrading the elastic modulus (rigidity) and heat resistance.
  • the polymer microparticle-dispersed resin composition provides cured products or polymerized products having excellent rigidity, heat resistance, toughness, and impact resistance in a good balance.
  • FIG. 1 is a transmission electron microscope photograph of a cured plate of Example 4.
  • the polymer microparticle-dispersed resin composition of the present invention contains: 100 parts by weight of a resin; and 0.1 parts by weight to 150 parts by weight of polymer microparticles each including at least two layers including a crosslinked polymer layer and a coating polymer layer, the resin composition having a particle dispersity of the polymer microparticles in the resin of not lower than 50%, the crosslinked polymer layer including 50% by weight to 99% by weight of at least one monomer having a Tg, as determined as a homopolymer, of not lower than 0° C., and 50% by weight to 1% by weight of at least one monomer having a Tg, as determined as a homopolymer, of lower than 0° C.
  • the polymer microparticle-dispersed resin composition of the present invention When the resin in the polymer microparticle-dispersed resin composition of the present invention is cured or polymerized product, the polymer microparticle-dispersed resin composition is provided with toughness and impact resistance almost or completely without degrading the elastic modulus and heat resistance of the resin.
  • the polymer microparticle-dispersed resin composition improves the toughness and impact resistance of the resin almost or completely without degrading the elastic modulus and heat resistance.
  • the present inventors found that when the resin in the polymer microparticle-dispersed resin composition is cured or polymerized to form a structure in which the polymer microparticles are dispersed as primary particles in the resin that is solid at ordinary temperature, the toughness and impact resistance of the resin are improved almost or completely without degrading the elastic modulus and heat resistance.
  • the present invention is based on this finding.
  • a preferred example of usable resins is at least one selected from the group consisting of curable or polymerizable monomers, curable or polymerizable oligomers, and thermoplastic polymers.
  • the resin is at least one selected from the group consisting of curable monomers, polymerizable monomers, curable oligomers, polymerizable oligomers, and thermoplastic polymers, and is liquid at ordinary temperature.
  • the polymer microparticle-dispersed resin composition of the present invention can be, optionally after diluted with an appropriate polymerizable or curable resin, cured or polymerized into cured products of various shapes which have remarkably improved rigidity and toughness.
  • Preferred examples of the monomers or oligomers include organic compounds containing a polymerizable or curable functional group, and the polymerizable or curable functional groups is preferably at least one selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, a carbon-carbon double bond, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group.
  • compounds having any of an epoxy group, an oxetane group, a phenolic hydroxyl group, a cyclic ester, a cyanate ester, a benzoxazine group, and a carbon-carbon double bond are preferable in terms of the range of their potential applications as polymerizable/curable resins, and compounds having an epoxy group (so-called epoxy resins) are particularly preferable.
  • Examples of usable epoxy resins include glycidyl ether-substituted compounds having a known basic skeleton compound such as a bisphenol compound, a hydrogenerated bisphenol compound, a phenol or o-cresol novolac, an aromatic amine, a polycyclic aliphatic or aromatic compound; and compounds having a cyclohexene oxide skeleton.
  • a bisphenol compound a hydrogenerated bisphenol compound, a phenol or o-cresol novolac, an aromatic amine, a polycyclic aliphatic or aromatic compound
  • compounds having a cyclohexene oxide skeleton such as a bisphenol compound, a hydrogenerated bisphenol compound, a phenol or o-cresol novolac, an aromatic amine, a polycyclic aliphatic or aromatic compound; and compounds having a cyclohexene oxide skeleton.
  • bisphenol A diglycidyl ether and condensates thereof are preferable.
  • thermoplastic polymers include acrylic resins, styrene resins, saturated polyester resins, and polycarbonate resins.
  • the polymer microparticle-dispersed resin composition of the present invention should contain 0.1 parts by weight to 150 parts by weight of polymer microparticles relative to 100 parts by weight of the resin as described above.
  • the amount of the polymer microparticles is preferably 1 part by weight to 100 parts by weight, and more preferably 2 parts by weight to 50 parts by weight in terms of providing toughness and impact resistance and ensuring the dispersibility of primary particles (which is attributed to the aforementioned properties) and for cost reasons.
  • the polymer microparticle-dispersed resin composition of the present invention has a particle dispersity of the polymer microparticles in the resin of not lower than 50%.
  • the expression “polymer microparticles are dispersed as primary particles” used herein means that the particle dispersity is not lower than 50%, and the polymer microparticles do not aggregate, namely they are separated from one another in the resin.
  • the particle dispersity (%) is calculated as described below by the following equation 1.
  • the particle dispersity is preferably not lower than 75%, and more preferably not lower than 90% in terms of improving the toughness.
  • Particle dispersity (%) (1 ⁇ ( B 1 /B 0 )) ⁇ 100 (equation 1)
  • the polymer microparticles dispersed as primary particles in the resin produces the effect of improving the toughness and impact resistance.
  • the polymer microparticles should be incompatible with the resin, in other word, should have a crosslinked polymer layer.
  • Each polymer microparticle should include a crosslinked polymer layer, and this allows the polymer microparticles to be incompatible with the resin and dispersed as primary particles.
  • the crosslinked polymer layer is a main structure component of the polymer microparticles, and preferably constitutes not less than 40% by weight, more preferably not less than 50% by weight of each polymer microparticle as a whole in terms of improving the toughness and impact resistance. The percentage is preferably not more than 95% by weight, and more preferably not more than 90% by weight.
  • each polymer microparticle has one or two or more crosslinked polymer layers in the inside in terms of improving the toughness and impact resistance.
  • the polymer microparticles further include a coating polymer layer that is the outermost layer for improving the dispersibility in the resin.
  • a coating polymer layer that is the outermost layer for improving the dispersibility in the resin.
  • Such a structure including inner crosslinked polymer layer(s) and an outermost coating polymer layer is called a “core/shell structure”, and the crosslinked polymer layer and the coating polymer layer are also called “core layer” and “shell layer”, respectively.
  • the coating polymer layer preferably constitutes not more than 50% by weight, and more preferably not more than 45% by weight of each polymer microparticle as a whole. Additionally, the percentage is preferably not less than 5% by weight, and more preferably not less than 10% by weight.
  • the coating polymer layer is the outermost of the polymer microparticles, and has an average thickness of not more than 20 nm. In order to improve the dispersibility, the average thickness thereof is more preferably 2 nm to 10 nm.
  • the crosslinked polymer layer is not limited at all, as long as the crosslinked polymer layer includes a crosslinked polymer containing at least one monomer having a Tg, as determined as a homopolymer, of not lower than 0° C., and at least one monomer having a Tg, as determined as a homopolymer, of lower than 0° C., and the crosslinked polymer contains 50% by weight to 99% by weight of the monomer having a Tg, as determined as a homopolymer, of not lower than 0° C., and 50% by weight to 1% by weight of the monomer having a Tg, as determined as a homopolymer, of lower than 0° C.
  • the crosslinked polymer layer preferably includes at least a crosslinked polymer layer including not less than 60% by weight of the monomer having a Tg, as determined as a homopolymer, of not lower than 0° C., and a crosslinked polymer layer including not less than 60% by weight of the monomer having a Tg, as determined as a homopolymer, of lower than 0° C. It is particularly preferable that the crosslinked polymer layer including not less than 60% by weight of the monomer having a Tg, as determined as a homopolymer, of not lower than 0° C.
  • the crosslinked polymer preferably has a gel content of not less than 70% by mass, more preferably not less than 90% by mass, and particularly preferably not less than 95% by mass.
  • gel content herein refers to a ratio of insoluble matter relative to the total amount of the insoluble matter and soluble matter in a sample prepared by immersing 0.5 g of aggregated and dried crumbs into 100 g of toluene, leaving the mixture standing at 23° C. for 24 hours, and separating the insoluble matter and the soluble matter.
  • the monomer having a Tg, as determined as a homopolymer, of not lower than 0° C. is at least one selected from, but not limited to, the following monomers: unsubstituted vinyl aromatics such as styrene and 2-vinylnaphthalene; vinyl substituted aromatics such as ⁇ -methyl styrene; ring-alkylated vinyl aromatics such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene; ring-alkoxylated vinyl aromatics such as 4-methoxystyrene and 4-ethyoxystyrene; ring-halogenated vinyl aromatics such as 2-chlorostyrene and 3-chrolostyrene; ring-ester-substituted vinyl aromatics such as 4-acetoxystyrene;
  • the Tg as determined as a homopolymer, is preferably not lower than 20° C., more preferably not lower than 50° C., and particularly preferably not lower than 80° C. in terms of preventing rigidity degradation.
  • Examples of monomers having a Tg, as determined as a homopolymer, of lower than 0° C. include, but not limited to, monomers constituting a diene rubber polymer, an acrylic rubber polymer, an organosiloxane rubber polymer, a polyolefin rubber (a polymer of an olefin compound), an aliphatic polyester (e.g. polycaprolactone), and a polyether (e.g. polyethylene glycol and polypropylene glycol).
  • Monomers constituting a diene rubber polymer, an acrylic rubber polymer, or an organosiloxane rubber polymer are more preferable for easy preparation of a crosslinked polymer aqueous dispersion.
  • monomers from which an acrylic rubber polymer is derived are preferable for easy polymerization in an aqueous environment.
  • the diene rubber polymers are polymers mainly formed from a diene monomer, and may be copolymers polymerized appropriately using later-described other vinyl monomer(s).
  • polyorganosiloxane particles prepared by a method such as solution polymerization, suspension polymerization, or emulsion polymerization in the presence of a catalyst such as an acid, an alkali, a salt, or a fluorine compound using cyclic siloxanes such as 1,3,5,7-octamethyl cyclotetrasiloxane (D4), preferably, a monomer for an organosiloxane rubber polymer mainly consisting of a liner or branched organosiloxane oligomer having a weight average molecular weight of 500 to 20,000 or smaller.
  • a catalyst such as an acid, an alkali, a salt, or a fluorine compound using cyclic siloxanes such as 1,3,5,7-octamethyl cyclotetrasiloxane (D4)
  • D4 1,3,5,7-octamethyl cyclotetrasiloxane
  • butadiene is not included in the scope of the term “polyfunctional monomer”, and examples of the polyfunctional monomer include allylalkyl (meth)acrylates such as allyl (meth)acrylate and allylalkyl (meth)acrylate; polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; and diallyl phthalate, triallyl cyanurate, triallyl isocyanurate (TAIL), glycidyl diallylisocyanurate, and divinyl benzene. Allyl methacrylate, triallyl isocyanurate, and divinyl benzene (DVB) are particularly preferable.
  • allylalkyl (meth)acrylates such as allyl (
  • allyl methacrylate (ALMA), TAIC, and diallyl phthalate are particularly preferable for the crosslinked polymer layer in terms of availability, ease of polymerization, and high grafting efficiency of an intermediate polymer layer (the outermost layer among crosslinked polymer layers of the core layer, or a layer between the crosslinked polymer layer including not less than 60% by weight of the monomer having a Tg, as determined as a homopolymer, of not lower than 0° C. and the crosslinked polymer layer including not less than 60% by weight of the monomer having a Tg, as determined as a homopolymer, of lower than 0° C. in the case where the core layer includes these layers) or the coating polymer layer.
  • an intermediate polymer layer the outermost layer among crosslinked polymer layers of the core layer, or a layer between the crosslinked polymer layer including not less than 60% by weight of the monomer having a Tg, as determined as a homopolymer, of not lower than 0° C. and the crosslinked polymer
  • the coating polymer layer contains a coating polymer layer polymer that is polymerized from a coating polymer layer component monomer.
  • the coating polymer layer polymer is not limited at all, as long as it improves the dispersibility of the polymer microparticles in the resin, and preferred examples thereof include vinyl polymers obtained by radical polymerization of vinyl group-containing vinyl monomer(s), polyolefins obtained by polymerization of olefin compound(s), silicone polymers obtained by polycondensation of siloxane compound(s), aliphatic polyesters such as polycaprolactone, and polyethers such as polyethylene glycol and polypropylene glycol.
  • vinyl polymers are preferable for the coating polymer layer because they can be graft polymerized to the crosslinked polymer layer.
  • the coating polymer layer preferably contains a monomer containing a polymerizable or curable functional group in addition to functional group(s) for the polymer main chain.
  • the polymerizable or curable functional group is preferably at least one selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, a carbon-carbon double bond, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, acyclic amide, a benzoxazine group, and a cyanate ester group.
  • the polymer preferably contains a vinyl monomer having the above-mentioned functional group in addition to a vinyl group for the main chain, in an amount of 0.1% by weight to 50% by weight relative to 100% by weight of the coating polymer layer components.
  • emulsifiers usable in the emulsion polymerization: various acids including alkyl or aryl sulfonic acids such as dioctylsulfosuccinic acid and dodecylbenzenesulfonic acid, alkyl or arylether sulfonic acids, alkyl or arylsulfuric acids such as dodecylsulfuric acids, alkyl or arylether sulfuric acids, alkyl or aryl-substituted phosphoric acids, alkyl or arylether-substituted phosphoric acids, N-alkyl or arylsarcosinic acids such as dodecylsarcosinic acid, alkyl or arylcarboxylic acids such as oleic acid and stearic acid, and alkyl or arylether carboxylic acids, and anionic emulsifiers (dispersants) usable in the emulsion polymerization: various acids
  • the amount of the emulsifier (dispersant) is preferably as small as possible, but the dispersion stability of the polymer microparticles in the aqueous latex should be secured.
  • the emulsifier (dispersant) preferably has as high water solubility as possible. An emulsifier (dispersant) having high water solubility can be easily washed out with water, and thus its bad influence on the final polycondensed product can be easily avoided.
  • the polymer microparticle-dispersed resin composition of the present invention may optionally contain oxidation inhibitors, ultraviolet absorbers, inorganic fillers, dyes, pigments, diluents, coupling agents, resins other than resins mentioned below as preferable resins, and the like, as long as they do not impair the original mechanical strength and toughness of the resin.
  • the polymer microparticle-dispersed resin composition of the present invention is suitably used as a molding material, an adhesive, a fiber or filler reinforced composite material, a sealing material, a casting material, an insulating material, a coating material, a filler, a stereolithography material, an optical component, an ink, or a toner.
  • the polymer microparticle-dispersed resin composition of the present invention can be cured, for example, by known curing methods using an action of a curing agent or a catalyst, heat or light (e.g. ultraviolent rays), or radiation rays (e.g. electron rays), or a combination of these.
  • heat or light e.g. ultraviolent rays
  • radiation rays e.g. electron rays
  • molding methods there may be mentioned transfer molding, injection molding, cast molding, coating and baking, rotary molding, stereolithography, hand lay-up molding using carbon fibers, glass fibers, or the like, prepreg molding, pultrusion, filament winding molding, press molding, resin transfer molding (RTM or VaRTM), and SMC molding.
  • the method for preparing the polymer microparticle-dispersed composition of the present invention includes, in sequence, the first step of obtaining loose aggregates of the polymer microparticles; the second step of obtaining a polymer microparticle dispersion; and the third step of obtaining a polymer microparticle-dispersed composition of the present invention.
  • the polymer microparticle-dispersed resin composition of the present invention is prepared successively through the first step of mixing an aqueous medium dispersion containing polymer microparticles dispersed in an aqueous medium with an organic solvent having a water solubility at 20° C.
  • the method for preparing the polymer microparticle-dispersed resin composition of the present invention is a simple method of preparing a polymer microparticle-dispersed resin composition in which polymer microparticles, the particle size is preferably 10 nm to 1000 nm, are dispersed well in any solid or liquid organic medium.
  • the first step involves mixing the aqueous medium dispersion and an organic solvent having a water solubility at 20° C. of preferably not lower than 5% by mass and not higher than 40% by mass (preferably not higher than 30% by mass).
  • an organic solvent having a water solubility at 20° C. of preferably not lower than 5% by mass and not higher than 40% by mass (preferably not higher than 30% by mass).
  • the organic solvent used in the first step may be an organic solvent mixture as long as the entire mixture has a water solubility at 20° C. of not lower than 5% by mass and not higher than 40% by mass.
  • a mixture of two or more selected from both low water-soluble organic solvents and high water-soluble organic solvents include ketones (e.g. methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, and ethyl butyl ketone), esters (e.g. diethyl carbonate, butyl formate, propyl acetate, and butyl acetate), ethers (e.g.
  • the organic solvent used in the first step is preferably one having a specific gravity of lower than that of water.
  • the amount of the organic solvent to be mixed with the aqueous latex is preferably not less than 50 parts by mass, and more preferably not less than 60 parts by mass relative to 100 parts by mass of the aqueous latex.
  • the amount is preferably not more than 250 parts by mass, and more preferably not more than 150 parts by mass. If the amount of the organic solvent is less than 50 parts by mass, the polymer microparticles in the aqueous latex are less likely to aggregate. If the amount of the organic solvent is more than 250 parts by mass, more water is required in the subsequent procedure for obtaining loose aggregates of the polymer microparticles, resulting in lower production efficiency.
  • a known technique can be used for the mixing procedure of the aqueous latex and the organic solvent.
  • a common device such as a stirring tank with a stirring blade may be used, or a static mixer or a line mixer (a system in which a stirrer is incorporated as a part of a pipeline) may be used.
  • the first step further involves, after the procedure of mixing the aqueous latex and the organic solvent, mixing the mixture with excess water. This procedure results in phase separation, which allows the polymer microparticles to aggregate into loose aggregates. At the same time, almost all electrolytic substances such as the water-soluble emulsifier or dispersant used for the preparation of the aqueous latex, a water-soluble polymerization initiator, and/or a reducing agent are eluted to the aqueous phase.
  • the amount of water to be used is preferably not less than 40 parts by mass, and more preferably not less than 60 parts by mass relative to 100 parts by mass of the organic solvent mixed with the aqueous latex. Additionally, the amount is preferably not more than 300 parts by mass, and more preferably not more than 250 parts by mass. If the amount of water is less than 40 parts by mass, it is difficult to obtain polymer microparticles as loose aggregates. If the amount of water is more than 300 parts by mass, the organic solvent concentration of the polymer microparticles becomes low, leading to low dispersibility of the polymer microparticles which can be seen as, for example, a prolonged time for re-dispersion of the aggregated polymer microparticles in the second step described below.
  • the separation and recovery of the aggregated polymer microparticles from the liquid phase can be accomplished by, for example, a method involving discharging the liquid phase (aqueous phase in many cases) from the bottom part of the stirring tank or a method involving filtering the liquid phase using a filter paper, a filter cloth, or a metal screen with relatively coarse meshes since aggregated polymer microparticles generally float to the surface of the liquid phase.
  • the second step further involves mixing the aggregates of the polymer microparticles (polymer microparticle dope) with an organic solvent.
  • the aggregates of the polymer microparticles are loose enough to be easily re-dispersed as primary particles in the organic solvent when mixed with the organic solvent.
  • Examples of the organic solvent used in the second step include those mentioned above as examples of organic solvents usable in the first step.
  • the use of such an organic solvent enables water contained in the polymer microparticles to be azeotropically distilled off with the organic solvent in the third step described below.
  • the organic solvent used in the second step may be different from the organic solvent used in the first step; however, the same organic solvent as that used in the first step is preferably used in terms of further ensuring re-dispersion of the aggregates.
  • the step of separating and recovering the aggregated polymer microparticles from the liquid phase mixing the polymer microparticles with the organic solvent having a water solubility at 20° C. of not lower than 5% by mass and not higher than 40% by mass again, and then further mixing the mixture with excess water to cause the polymer microparticles to aggregate into loose aggregates of the polymer microparticles between the first step and the second step.
  • This further reduces the residual amount of water-soluble foreign substances such as an emulsifier contained in the polymer microparticle dope.
  • the amount of the resin used in the third step can be properly adjusted based on the desired polymer microparticle concentration in a polymer microparticle-dispersed resin composition to be finally obtained.
  • the organic solvent can be evaporated by known methods. Examples of such methods include a method involving loading a mixture of the dispersion of the polymer microparticles (organic solvent solution) and the resin into a tank, and heating the mixture under reduced pressure to remove the organic solvent; a method involving counter-flow contact of a drying gas and the mixture described above in a tank; a continuous method using a thin film type evaporator or the like; and a method using an extruder or a continuous stirring tank equipped with an evaporation mechanism.
  • the conditions for evaporation of the organic solvent such as the temperature and time, can be properly selected not to affect the quality of the polymer microparticle-dispersed resin composition to be obtained. Further, the amount of volatile matter remaining in the polymer microparticle-dispersed resin composition can be properly set not to hinder the use of the polymer microparticle-dispersed resin composition for desired applications.
  • a combination of the polymer microparticle-dispersed resin composition of the present invention and reinforcing fibers provides a fiber reinforced composite material or a prepreg (precursor thereof) which have remarkably improved toughness and impact strength almost or completely without degrading rigidity, heat resistance, and the like.
  • reinforcing fibers usable in the present invention include glass fibers, carbon fibers, aramid fibers, boron fibers, and alumina fibers. Among these, carbon fibers are particularly preferable.
  • each polymer microparticle-dispersed resin composition was out, and polymer microparticles were dyed with ruthenium oxide or osmium oxide.
  • the dyed samples were sliced to obtain ultra-thin sections, and the ultra-thin sections were observed at 10000 and 40000 times magnification with a transmission electron microscope (JEM-1200 EX, product of JEOL Ltd.).
  • the particle dispersity (%) was calculated as described below.
  • the fracture toughness Klc (MPa ⁇ m 1/2 ) was calculated by the following equations 3 and 4 using the maximum strength F (kN) determined by the bending test.
  • a is the sum of the depth of the V notch and the distance from the tip of the V notch to the crack front, and all the units of L, h, a, and b are “cm” (ASTM D5045).
  • test sample length and width: 4 cm, thickness: 3 mm
  • the 50% breaking height was determined by performing a test in accordance with JIS K 7211 using Dupont Impact Tester (product of Yasuda Seiki seisakusho LTD.) with a 500-g weight and a punch with a radius of 1 ⁇ 4 inch.
  • a sample (each side of which was not longer than 0.5 mm) was cut out from a cured plate sample, and an about 10 mg portion thereof was put on a measurement container of a differential scanning calorimetry, DSC 220C (product of Seiko Instruments Inc.), and measured for glass transition temperature at a temperature increasing rate of 10° C./min (JIS K 7121).
  • the extrapolated onset glass transition temperature was defined as the glass transition temperature.
  • a pressure-resistant polymerization reactor 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by mass of ferrous sulfate heptahydrate, and 1.55 parts by mass of sodium dodecylbenzenesulfonate (SDBS) were charged, and stirred while sufficiently purging with nitrogen to remove oxygen. Then, 100 parts by mass of butadiene (Bd) was fed to the system, and the mixture was heated to 45° C.
  • Bd butadiene
  • aqueous latex including a crosslinked polymer layer mainly made of polybutadiene (corresponding to 83 parts by mass of polybutadiene rubber particles) and 58 parts by mass of deionized water were charged, and stirred at 60° C. while purging with nitrogen.
  • aqueous latex (L-1) containing polymer microparticles was obtained.
  • the polymerization conversion ratios of the monomer components were not lower than 99%.
  • Polymer microparticles in the obtained aqueous latex had a volume average particle size of 100 nm.
  • aqueous latex (L-5) containing polymer microparticles was prepared in the same manner as in Preparation 2, except that a mixture of 58 parts by mass of MMA, 1.09 parts by mass of ALMA, and 0.017 parts by mass of CHP was continuously added dropwise over 140 minutes, and after 0.5 hours, a mixture of 25 parts by mass of BA, 0.47 parts by mass of ALMA, and 0.007 parts by mass of CHP was continuously added dropwise over 60 minutes instead of continuously adding dropwise the mixture of 83 parts by mass of St, 1.56 parts by mass of ALMA, and 0.024 parts by mass of CHP over 200 minutes. All the polymerization conversion ratios of the monomer components were not lower than 99%. Polymer microparticles in the obtained aqueous latex had a volume average particle size of 95 nm.
  • aqueous latex (L-7) containing polymer microparticles was prepared in the same manner as in Preparation 2, except that a mixture of 73 parts by mass of St, 1.37 parts by mass of ALMA, and 0.021 parts by mass of CHP were continuously added dropwise over 175 minutes, and after 0.5 hours, a mixture of 10 parts by mass of 2EHA, 0.19 parts by mass of ALMA, and 0.003 parts by mass of CHP was continuously added dropwise over 25 minutes instead of continuously adding dropwise the mixture of 83 parts by mass of St, 1.56 parts by mass of ALMA, and 0.024 parts by mass of CHP over 200 minutes. All the polymerization conversion ratios of the monomer components were not lower than 99%. Polymer microparticles in the obtained aqueous latex had a volume average particle size of 123 nm.
  • Table 1 shows the monomer compositions of Preparations 1 to 7 together.
  • a liquid resin composition was prepared by mixing well 97.6 g of a liquid bisphenol A epoxy resin (“JER 828EL”, product of JER, epoxy equivalent weight; 187 g/eq) and 32.4 g of diaminodiphenylsulfone (curing agent, “Aradur 9664-1”, product of Huntsman, active amine equivalent weight; 62 g/eq) at a constant temperature of 130° C., and defoaming the mixture.
  • This liquid resin composition was charged between two glass plates spaced therebetween with a 5-mm thick spacer, and cured in a hot air oven at 150° C. for 1 hour, and then at 180° C. for 2 hours. In this manner, a 5-mm thick cured plate 1 was obtained.
  • Table 2 shows the physical property values of the cured plate 1.
  • a liquid resin composition was prepared by mixing well 16.25 g of a bisphenol A epoxy adduct of carboxyl group-terminated butadiene-acrylonitrile copolymer rubber (CTBN) (“EPON 58006”, product of Hexion, CTBN content: 40 wt %) 82.95 g of a liquid bisphenol A epoxy resin, JER 828EL, and 30.8 g of diaminodiphenylsulfone, Aradur 9664-1 (curing agent) at a constant temperature of 130° C., and then defoaming the mixture.
  • This liquid resin composition was charged between two glass plates spaced therebetween with a 5-mm thick spacer, and cured in a hot air oven at 150° C. for 1 hour, and then at 180° C. for 2 hours. In this manner, a 5-mm thick cured plate 2 was obtained.
  • Table 2 shows the physical property values of the cured plate
  • aqueous latex (L-1) containing polymer microparticles obtained in Preparation 1 was also charged under stirring. After homogeneously mixing them, 200 parts by mass of water was added at a feeding rate of 80 parts by mass/min (the total amount: 452 parts by mass). Immediately after the whole amount was added, the stirring was stopped. Thus, a slurry containing buoyant aggregates was obtained. Next, 350 parts by mass of the liquid phase was discharged through a discharge port at a lower portion of the tank, while leaving the aggregates.
  • MEK methyl ethyl ketone
  • a resin composition was prepared by mixing well 65 g of this polymer microparticle-dispersed resin composition 1 (epoxy equivalent weight; 208 g/eq) (containing 6.5 g of polymer microparticles), 34.2 g of JER 828EL, and 30.8 g of diaminodiphenylsulfone (curing agent, Aradur 9664-1) at a constant temperature of 130° C. (the mixture contained 5% by weight of polymer microparticles), and defoaming the mixture.
  • This liquid resin composition was charged between two glass plates spaced therebetween with a 5-mm thick spacer, and cured in a hot air oven at 150° C. for 1 hour, and then at 180° C. for 2 hours. Consequently, a 5-mm thick cured plate 3 was obtained.
  • Table 2 shows the physical property values of this cured plate 1.
  • Bisphenol A epoxy resins containing polymer microparticles dispersed therein were obtained as polymer microparticle-dispersed resin compositions 2 to 7 in the same manner as in Comparative Example 3, except that the aqueous latexes (L-2 to L-7) of polymer microparticles prepared in Preparations 2 to 7 were used instead of the aqueous latex L-1 used in Comparative Example 3.
  • cured plates 4 to 9 were obtained in the same manner as in Comparative Example 3 from the polymer microparticle-dispersed resin compositions 2 to 7, respectively.
  • the obtained cured plates 4 to 9 correspond to Comparative Examples 4 to 5 and Examples 1 to 4, respectively.
  • Table 2 shows the physical property values of the cured plates 4 to 9.
  • Example 4 showed high fracture toughness and impact strength, and was excellent in the balance of the physical properties.
  • the cured plate obtained in Example 4 was treated by the above-mentioned method, specifically was cut with a microtome to obtain an ultra-thin section sample, and the sample was dyed with ruthenium oxide, and observed with a transmission electron microscope to evaluate dispersed polymer microparticles and calculate the particle dispersity.
  • the microscope photograph was shown as FIG. 1 .
  • the particle dispersity was 89%. Specifically, it was confirmed that polymer microparticles were not agglomerated and were dispersed as primary particles in the polymer microparticle-dispersed composition.
  • CFRPs including the polymer microparticle-dispersed resin compositions of Examples and Comparative Examples and carbon fibers, and the results of the evaluation.
  • a bisphenol A epoxy resin containing polymer microparticles dispersed therein was prepared as a polymer microparticle-dispersed resin composition 8 (containing 25% by weight of polymer microparticles) in the same manner as in Comparative Example 3, except that the amount of the organic solvent solution was changed from 71.6 parts by mass (containing 11.1 parts by weight of polymer microparticles) to 214.8 parts by mass (containing 33.3 parts by weight polymer), and Epo Tohto YD-128 was used instead of JER 828EL.
  • a bisphenol A epoxy resin containing polymer microparticles dispersed therein was prepared as a polymer microparticle-dispersed resin composition 9 (containing 25% by weight of polymer microparticles) in the same manner as in Comparative Example 3, except that the aqueous latex (L-7) of polymer microparticles obtained in Preparation 7 was used instead of the aqueous latex (L-1) of polymer microparticles obtained in Preparation 1, the amount of the organic solvent solution was changed from 71.6 parts by mass (containing 11.1 parts by weight of polymer microparticles) to 214.8 parts by mass (containing 33.3 parts by weight of polymer microparticles), and Epo Tohto YD-128 was used instead of JER 828EL.
  • a prepreg resin composition 3 was prepared by stirring and mixing 40 parts by weight of the polymer microparticle-dispersed resin composition 9, 15 parts by weight of Epo Tohto YD-128, 25 parts by weight of Epo Tohto YD-012, and 30 parts by weight of Epo Tohto YDCN-700-7 together at 100° C., cooling the mixture to 70° C., and adding 4.0 parts by weight of jER cure DICY7 and 2.5 parts by weight of DCMU and stirring and mixing the mixture.
  • a VaRTM resin composition 1 was prepared by mixing 100 parts by weight of Epo Tohto YD-128, 85 parts by weight of methylnadic anhydride (NMA, Wako Pure Chemical Industries, Ltd.), and 1.0 part by weight of 2-ethyl-4-methyl imidazole (“CUREZOL 2E4MZ”, product of SHIKOKU CHEMICALS CORPORATION).
  • a VaRTM resin composition 2 was prepared by mixing 36 parts by weight of the polymer microparticle-dispersed resin composition 8 obtained in the process of preparation of the prepreg resin composition 2, 64 parts by weight of Epo Tohto YD-128, 77 parts by weight of NMA, and 0.9 parts by weight of CUREZOL 2E4MZ.
  • a VaRTM resin composition 3 was prepared by mixing 36 parts by weight of the polymer microparticle-dispersed resin composition 9 obtained in the process of preparation of the prepreg resin composition 3, 64 parts by weight of Epo Tohto YD-128, 77 parts by weight of NMA, and 0.9 parts by weight of CUREZOL 2E4MZ.
  • Carbon fibers (“ECS6090”, product of Saertex) were stacked with a [(0/90)] 5s configuration (a Teflon-coated polyimide film (“Kapton 120HR616”, product of DU PONT-TORAY CO., LTD.) was inserted on a portion of exactly the middle layer in this configuration).
  • Each of the VaRTM resin compositions 1 to 3 obtained in the process (1) was poured onto the stack by VaRTM method, and cured at 80° C. for 2 hours, and then post-cured at 135° C. for 4 hours.
  • CFRPs 1 to 3 having a thickness of 2.8 mm were obtained.
  • the unidirectional prepregs 1 to 3 obtained in the process (2) were each cut into pieces of a predetermined size, and 24 pieces of each prepreg were stacked in the same orientation (Kapton 120HR616 was inserted on a portion of exactly the middle layer (the 12th layer) in this configuration), wrapped with a Teflon-coated PET film, and cured at 125° C. for 1 hour using a press molder under a pressure of 3 kg/cm 2 .
  • unidirectional CFRPs having a fiber volume content (Vf) of 53% and a thickness of 3 mm were obtained.
  • the unidirectional CFRPs were each cut into a sample having a width of 21.5 mm (in the direction perpendicular to the fiber orientation) and a length of 140 mm (in the direction parallel to the fiber orientation) in which the polyimide film insertion part was 45 mm long from the edge. Then, the polyimide film was removed. Subsequently, a wedge was hit with a plastic hammer at the opening of the film insertion part, so that a precrack having a length of about 2 mm was formed. In this manner, samples for the mode II interlaminar fracture toughness test (unidirectional CFRPs 1 to 3) were obtained. The test was performed in accordance with JIS K 7086.
  • Unidirectional CFRPs were obtained in the same manner as in the process (5), and cut into samples having a length of 15 mm (in the direction parallel to the fiber orientation) and a width of 100 mm (in the direction perpendicular to the fiber orientation). In this manner, samples for the 90° flexural modulus test (unidirectional CFRPs 7 to 9) were obtained. The test was performed in accordance with JIS K 7074.

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EP2662414A1 (fr) 2013-11-13
JP5940462B2 (ja) 2016-06-29
CN103282442B (zh) 2016-06-08
CA2822596A1 (fr) 2012-07-12
EP2662414B1 (fr) 2018-04-11
WO2012093631A1 (fr) 2012-07-12
MY162805A (en) 2017-07-14
KR20140007369A (ko) 2014-01-17

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